JP2010147237A - Method of manufacturing wiring structure, and wiring structure - Google Patents

Method of manufacturing wiring structure, and wiring structure Download PDF

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JP2010147237A
JP2010147237A JP2008322660A JP2008322660A JP2010147237A JP 2010147237 A JP2010147237 A JP 2010147237A JP 2008322660 A JP2008322660 A JP 2008322660A JP 2008322660 A JP2008322660 A JP 2008322660A JP 2010147237 A JP2010147237 A JP 2010147237A
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wiring
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horizontal
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film
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JP5572944B2 (en
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Daiyu Kondo
大雄 近藤
Shintaro Sato
信太郎 佐藤
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Fujitsu Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem of difficulty in forming a catalyst film that has a flat and minute surface on its sidewall so as to grow a carbon nanotube in a lateral direction (a direction parallel to the surface of a substrate). <P>SOLUTION: A first thickness of catalytic layer for longitudinal wiring is formed in two longitudinal wiring areas 23 separated from each other on a substrate surface and, a second thickness of catalytic layer for lateral wiring is formed on a lateral wiring area continuous from one longitudinal wiring area to the other longitudinal wiring area, with the second thickness set larger than the first thickness. A structure containing carbon is vapor deposited on the catalytic layer for longitudinal wiring and the catalytic layer for lateral wiring. The first and second thicknesses are set so that, in the initial stage of vapor deposition, graphite grows on the catalytic layer for longitudinal wiring and the catalytic layer for lateral wiring, then, carbon nanotubes grow between the graphite on the longitudinal wiring areas and the substrate, and thereby, the graphite on the lateral wiring area is held in a space by the carbon nanotubes grown on the longitudinal wiring areas. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、縦方向の配線にカーボンナノチューブを用いた配線構造体及びその製造方法に関する。   The present invention relates to a wiring structure using carbon nanotubes for vertical wiring and a method for manufacturing the same.

半導体集積回路素子の配線材料として、主に銅（Ｃｕ）が用いられている。配線幅の微細化に伴い、エレクトロマイグレーションによる信頼性の劣化や電気抵抗の増大が顕在化してきている。これらの課題を解決するために、銅に代わる新しい配線材料として、カーボンナノチューブが注目されている。縦方向（基板の厚さ方向）の配線に、カーボンナノチューブを用いた配線構造が公知である。また、カーボンナノチューブ上に成長したグラファイト構造についても公知である。   Copper (Cu) is mainly used as a wiring material for semiconductor integrated circuit elements. As the wiring width becomes finer, deterioration of reliability and increase in electrical resistance due to electromigration have become apparent. In order to solve these problems, carbon nanotubes have attracted attention as a new wiring material that replaces copper. A wiring structure using carbon nanotubes for wiring in the vertical direction (thickness direction of the substrate) is known. A graphite structure grown on carbon nanotubes is also known.

特開２００７−２２０７４２号公報JP 2007-220742 A 特開２００８−１３７８４６号公報JP 2008-137846 A Daiyu Kondo et al., "Self-organization of Novel Carbon Composite Structure: Graphene Multi-Layers Combined Perpendicularly with Aligned Carbon Nanotubes", Applied Physics Express 1(2008) 074003Daiyu Kondo et al., "Self-organization of Novel Carbon Composite Structure: Graphene Multi-Layers Combined Perpendicularly with Aligned Carbon Nanotubes", Applied Physics Express 1 (2008) 074003

基板表面に対して垂直の方向にカーボンナノチューブを成長させることは比較的容易である。横方向（基板表面に平行な方向）にカーボンナノチューブを成長させるためには、側壁に平坦かつ微小な表面を持つ触媒膜を形成する必要がある。ところが、このような触媒膜を形成することは困難である。   It is relatively easy to grow carbon nanotubes in a direction perpendicular to the substrate surface. In order to grow carbon nanotubes in the lateral direction (direction parallel to the substrate surface), it is necessary to form a catalyst film having a flat and minute surface on the side wall. However, it is difficult to form such a catalyst film.

上記課題を解決する配線構造体の製造方法は、
基板表面の相互に離隔した２つの縦配線領域に、第１の厚さの縦配線用触媒膜を形成し、１つの該縦配線領域から他の縦配線領域まで連続する横配線領域に、該第１の厚さよりも厚い第２の厚さの横配線用触媒膜を形成する工程と、
前記縦配線用触媒膜及び横配線用触媒膜の上に、カーボンを含む構造体を気相成長させる工程と
を有し、
前記気相成長の初期段階には、前記縦配線用触媒膜及び横配線用触媒膜の上にグラファイトが形成され、その後、前記縦配線領域の前記グラファイトと前記基板との間にカーボンナノチューブが成長し、前記横配線領域の前記グラファイトが、前記縦配線領域に成長したカーボンナノチューブによって中空に支持されるように前記第１の厚さ及び第２の厚さが設定されている。 A method of manufacturing a wiring structure that solves the above problems is as follows.
A catalyst film for vertical wiring having a first thickness is formed in two vertical wiring regions separated from each other on the substrate surface, and the horizontal wiring region continuous from one vertical wiring region to another vertical wiring region Forming a lateral wiring catalyst film having a second thickness greater than the first thickness;
Vapor-phase-growing a structure containing carbon on the vertical wiring catalyst film and the horizontal wiring catalyst film,
In the initial stage of the vapor phase growth, graphite is formed on the vertical wiring catalyst film and the horizontal wiring catalyst film, and then carbon nanotubes grow between the graphite and the substrate in the vertical wiring region. The first thickness and the second thickness are set so that the graphite in the horizontal wiring region is supported in a hollow manner by the carbon nanotubes grown in the vertical wiring region.

上記課題を解決する配線構造体は、
基板の表面の複数の導電性領域の各々から延びる複数のカーボンナノチューブを含む縦配線と、
少なくとも２つの前記縦配線の一方の上端から他方の上端まで横方向に延びるグラファイトを含む横配線と
を有する。 A wiring structure that solves the above problems
A vertical wiring including a plurality of carbon nanotubes extending from each of a plurality of conductive regions on the surface of the substrate;
A horizontal wiring including graphite extending in a lateral direction from one upper end to the other upper end of at least two of the vertical wirings.

縦配線及び横配線の両方を、炭素材料で形成することにより、電流密度耐性を高めることができる。これにより、配線の微細化が容易になると共に、エレクトロマイグレーション耐性を高めることができる。   By forming both the vertical wiring and the horizontal wiring with a carbon material, the current density resistance can be increased. This facilitates miniaturization of the wiring and enhances electromigration resistance.

以下、図面を参照しながら、実施例を説明する。   Embodiments will be described below with reference to the drawings.

図１に、実施例１による配線構造体の斜視図を示す。表面に、複数の半導体素子及び配線が形成された基板１０の上に、複数の１層目の縦配線１１が形成されている。１層目の縦配線１１の各々は、基板１０の表面に対して垂直な方向に延びるカーボンナノチューブの束で構成されている。   FIG. 1 is a perspective view of a wiring structure according to the first embodiment. A plurality of first-layer vertical wirings 11 are formed on a substrate 10 on the surface of which a plurality of semiconductor elements and wirings are formed. Each of the vertical wirings 11 in the first layer is composed of a bundle of carbon nanotubes extending in a direction perpendicular to the surface of the substrate 10.

少なくとも２つの１層目の縦配線１１の上端同士を、１層目の横配線１２が接続している。１層目の横配線１２は、グラファイトで構成されており、１層目の縦配線１１によって中空に支持されている。１層目の横配線１２の上に、２層目の縦配線１３が形成されている。少なくとも２つの２層目の縦配線１３の上端同士を、２層目の横配線１４が接続する。さらに、３層目以上の縦配線及び横配線が形成されている。２層目以上の配線層においても、縦配線１３等はカーボンナノチューブで形成され、横配線１４等は、グラファイトで形成されている。２層目以上の横配線１４等は、それよりも下方の縦配線１１、１３、及び横配線１２により、中空に支持されている。   The upper ends of at least two first-layer vertical wirings 11 are connected to the first-layer horizontal wirings 12. The first-layer horizontal wiring 12 is made of graphite, and is supported in a hollow space by the first-layer vertical wiring 11. A second-layer vertical wiring 13 is formed on the first-layer horizontal wiring 12. The upper ends of at least two second-layer vertical wirings 13 are connected to the second-layer horizontal wirings 14. Further, a vertical wiring and a horizontal wiring of the third layer or more are formed. Also in the second and higher wiring layers, the vertical wiring 13 and the like are formed of carbon nanotubes, and the horizontal wiring 14 and the like are formed of graphite. The horizontal wirings 14 and the like in the second layer or more are supported in a hollow manner by the vertical wirings 11 and 13 and the horizontal wirings 12 below it.

図２Ａ〜図２Ｏを参照して、実施例１による配線構造体の製造方法について説明する。   With reference to FIGS. 2A to 2O, a method for manufacturing a wiring structure according to the first embodiment will be described.

図２Ａに示すように、基板１０の上に、ＴｉＮからなる厚さ１ｎｍ〜３０ｎｍ、例えば５ｎｍの導電膜２０を形成する。導電膜２０の上に、Ｃｏからなる厚さ２．６ｎｍの縦配線用触媒膜２１を形成する。導電膜２０及び縦配線用触媒膜２１の形成には、例えばマグネトロンスパッタリング法を適用することができる。なお、その他に、レーザアブレーション法、電子ビーム蒸着法、分子線エピタキシ（ＭＢＥ）法、化学気相成長（ＣＶＤ）法、原子層堆積（ＡＬＤ）法等を用いてもよい。   As shown in FIG. 2A, a conductive film 20 made of TiN and having a thickness of 1 nm to 30 nm, for example, 5 nm is formed on the substrate 10. On the conductive film 20, a 2.6 nm-thickness catalyst film 21 for vertical wiring made of Co is formed. For the formation of the conductive film 20 and the vertical wiring catalyst film 21, for example, a magnetron sputtering method can be applied. In addition, a laser ablation method, an electron beam evaporation method, a molecular beam epitaxy (MBE) method, a chemical vapor deposition (CVD) method, an atomic layer deposition (ALD) method, or the like may be used.

縦配線用触媒膜２１の表面のうち、１層目の縦配線を形成すべき領域（第１の縦配線領域）２３を覆うレジストパターン２２を形成する。第１の縦配線領域２３の平面形状は、例えば直径１００ｎｍの円形、または一辺の長さが１００ｎｍの正方形等である。１層目の縦配線を形成しない領域においては、縦配線用触媒膜２１が露出している。   A resist pattern 22 is formed to cover a region (first vertical wiring region) 23 in which the first-layer vertical wiring is to be formed on the surface of the vertical wiring catalyst film 21. The planar shape of the first vertical wiring region 23 is, for example, a circle having a diameter of 100 nm or a square having a side length of 100 nm. In the region where the first-layer vertical wiring is not formed, the vertical wiring catalyst film 21 is exposed.

図２Ｂに示すように、レジストパターン２２で覆われていない領域の縦配線用触媒膜２１及び導電膜２０を、イオンミリング等により除去する。図２Ｃに示すように、レジストパターン２２を除去する。第１の縦配線領域２３に、パターニングされた導電膜２０と縦配線用触媒膜２１とからなる積層構造が残る。なお、導電膜２０及び縦配線用触媒膜２１のパターニングには、リフトオフ法を用いてもよいし、化学的エッチングを用いてもよい。また、レジストが触媒金属と触れることによる汚染を避けるために、エッチングマスクとして、絶縁膜等によるハードマスクを用いることもできる。   As shown in FIG. 2B, the vertical wiring catalyst film 21 and the conductive film 20 in a region not covered with the resist pattern 22 are removed by ion milling or the like. As shown in FIG. 2C, the resist pattern 22 is removed. In the first vertical wiring region 23, a laminated structure including the patterned conductive film 20 and the vertical wiring catalyst film 21 remains. Note that the lift-off method or chemical etching may be used for patterning the conductive film 20 and the vertical wiring catalyst film 21. Further, in order to avoid contamination due to contact of the resist with the catalytic metal, a hard mask made of an insulating film or the like can be used as an etching mask.

図２Ｄに示すように、第１の縦配線領域２３、及び１層目の横配線を形成しない領域（第１の無配線領域）２５を覆うレジストパターン３０を形成する。１層目の横配線が形成される領域（第１の横配線領域）２６には、レジストパターン３０の開口３０Ａが形成されている。第１の横配線領域２６は、１つの第１の縦配線領域２３から他の第１の縦配線領域２３まで連続する。   As shown in FIG. 2D, a resist pattern 30 is formed to cover the first vertical wiring region 23 and the region (first non-wiring region) 25 where the first-layer horizontal wiring is not formed. An opening 30A of the resist pattern 30 is formed in a region (first lateral wiring region) 26 where the first-layer lateral wiring is formed. The first horizontal wiring region 26 is continuous from one first vertical wiring region 23 to another first vertical wiring region 23.

開口３０Ａの底面、及びレジストパターン３０の上面に、ＴｉＯ２からなる絶縁膜３４を形成し、その上にＣｏからなる厚さ４．５ｎｍの横配線用触媒膜３５を形成する。絶縁膜３４の厚さは、導電膜２０の厚さと等しくすることが好ましい。絶縁膜３４及び横配線用触媒膜３５の形成には、例えばマグネトロンスパッタリングが適用される。 An insulating film 34 made of TiO 2 is formed on the bottom surface of the opening 30A and on the upper surface of the resist pattern 30, and a 4.5 nm thick wiring wiring catalyst film 35 made of Co is formed thereon. The thickness of the insulating film 34 is preferably equal to the thickness of the conductive film 20. For example, magnetron sputtering is applied to the formation of the insulating film 34 and the lateral wiring catalyst film 35.

縦配線用触媒膜２１及び横配線用触媒膜３５に、カーボンナノチューブ形成のための触媒として作用するＣｏ以外の材料、例えばＮｉ、Ｆｅ、Ｐｔ、Ａｕ等を用いてもよい。導電膜２０に、Ｔｉ、ＴｉＳｉ、ＴｉＮ、Ｍｏ、Ｗ、Ｈｆ、Ｚｒ、Ａｌ、Ｎｂ、Ｖ、Ｔａ、ＴａＮ、ＴａＳｉのいずれか１つを含む導電材料を用いてもよい。絶縁膜３４に、Ｔｉ、ＴｉＳｉ、ＴｉＮ、ＴｉＯ２、Ｍｏ、Ｗ、Ｈｆ、Ｚｒ、Ａｌ、Ａｌ２Ｏ３、Ｎｂ、Ｖ、Ｔａ、ＴａＮ、ＴａＯ２のいずれか１つを含む絶縁材料を用いてもよい。導電膜２０及び絶縁膜３４は、縦配線用触媒膜２１及び横配線用触媒膜３５を構成する金属を担持する役割を持つ。 The vertical wiring catalyst film 21 and the horizontal wiring catalyst film 35 may be made of a material other than Co that acts as a catalyst for forming carbon nanotubes, such as Ni, Fe, Pt, or Au. A conductive material containing any one of Ti, TiSi, TiN, Mo, W, Hf, Zr, Al, Nb, V, Ta, TaN, and TaSi may be used for the conductive film 20. An insulating material including any one of Ti, TiSi, TiN, TiO 2 , Mo, W, Hf, Zr, Al, Al 2 O 3 , Nb, V, Ta, TaN, and TaO 2 is used for the insulating film 34. May be. The conductive film 20 and the insulating film 34 have a role of supporting the metal constituting the vertical wiring catalyst film 21 and the horizontal wiring catalyst film 35.

図２Ｅに示すように、レジストパターン３０を、その上に堆積している絶縁膜３４及び横配線用触媒膜３５と共に除去する。第１の横配線領域２６には、絶縁膜３４と横配線用触媒膜３５が残る。第１の縦配線領域２３には、縦配線用触媒膜２１が露出する。第１の無配線領域２５には、基板１０の表面が露出する。   As shown in FIG. 2E, the resist pattern 30 is removed together with the insulating film 34 and the lateral wiring catalyst film 35 deposited thereon. In the first lateral wiring region 26, the insulating film 34 and the lateral wiring catalyst film 35 remain. In the first vertical wiring region 23, the vertical wiring catalyst film 21 is exposed. The surface of the substrate 10 is exposed in the first non-wiring region 25.

その後、熱化学気相成長（熱ＣＶＤ）により、縦配線用触媒膜２１及び横配線用触媒膜３５の上に、炭素を成長させる。成長条件は、例えば下記の通りである。
・成長温度 ４５０℃
・原料ガス アルゴンで希釈したアセチレン（アセチレンの分圧比１０％）
・圧力 １ｋＰａ
図２Ｆに示すように、成長初期段階には、縦配線用触媒膜２１及び横配線用触媒膜３５の上に、グラファイト（横配線）１２が成長する。第１の無配線領域２５には、グラファイトが形成されない。成長を続けると、縦配線用触媒膜２１が炭素を吸収して微粒子状になる。 Thereafter, carbon is grown on the vertical wiring catalyst film 21 and the horizontal wiring catalyst film 35 by thermal chemical vapor deposition (thermal CVD). The growth conditions are, for example, as follows.
・ Growth temperature 450 ℃
-Source gas Acetylene diluted with argon (acetylene partial pressure ratio 10%)
・ Pressure 1kPa
As shown in FIG. 2F, graphite (lateral wiring) 12 grows on the vertical wiring catalyst film 21 and the horizontal wiring catalyst film 35 in the initial growth stage. Graphite is not formed in the first non-wiring region 25. As the growth continues, the vertical wiring catalyst film 21 absorbs carbon and becomes fine particles.

図２Ｇに示すように、横配線１２の厚さが２０ｎｍ程度になると、微粒子状になった触媒金属から下方に、カーボンナノチューブ１１Ａが成長する。カーボンナノチューブ１１Ａの束が縦配線１１を構成する。縦配線１１の高さは、例えば２００ｎｍとする。横配線用触媒膜３５は、縦配線用触媒膜２１よりも厚く形成されているため、微粒子状にならず、その下にカーボンナノチューブは成長しない。縦配線１１が成長すると、横配線１２が上方に持ち上げられ、第１の横配線領域２６の横配線１２の下方に空洞が形成される。   As shown in FIG. 2G, when the thickness of the horizontal wiring 12 reaches about 20 nm, the carbon nanotube 11A grows downward from the catalyst metal in the form of fine particles. A bundle of carbon nanotubes 11 </ b> A constitutes the vertical wiring 11. The height of the vertical wiring 11 is, for example, 200 nm. Since the horizontal wiring catalyst film 35 is formed thicker than the vertical wiring catalyst film 21, it does not form fine particles, and carbon nanotubes do not grow thereunder. When the vertical wiring 11 grows, the horizontal wiring 12 is lifted upward, and a cavity is formed below the horizontal wiring 12 in the first horizontal wiring region 26.

図２Ｈに、縦配線１１及び横配線１２の断面図を示す。横配線１２の下側の表面に、縦配線用触媒膜２１の金属元素が微粒子状になった触媒微粒子２１ａが付着している。触媒微粒子２１ａから下方に向かって、カーボンナノチューブ１１Ａが延びている。図２Ｈでは、カーボンナノチューブ１１Ａが２層構造である場合を示しているが、単層のカーボンナノチューブまたは３層以上の多層カーボンナノチューブを形成してもよい。カーボンナノチューブ１１の太さは、例えば約１０ｎｍである。カーボンナノチューブ１１の太さは、触媒微粒子の直径や、触媒及び成長条件により制御可能であり、カーボンナノチューブ１１の太さを１〜５０ｎｍの範囲内にすることが望ましい。   FIG. 2H shows a cross-sectional view of the vertical wiring 11 and the horizontal wiring 12. On the lower surface of the horizontal wiring 12, catalyst fine particles 21a in which the metal element of the vertical wiring catalyst film 21 is formed into fine particles are attached. The carbon nanotubes 11A extend downward from the catalyst fine particles 21a. Although FIG. 2H shows a case where the carbon nanotube 11A has a two-layer structure, a single-walled carbon nanotube or a multilayered carbon nanotube of three or more layers may be formed. The thickness of the carbon nanotube 11 is, for example, about 10 nm. The thickness of the carbon nanotube 11 can be controlled by the diameter of the catalyst fine particles, the catalyst, and the growth conditions, and the thickness of the carbon nanotube 11 is preferably in the range of 1 to 50 nm.

図２Ｉに示すように、基板１０及び横配線１２の上に、酸化シリコン系の充填膜４０を、スピンオングラス（ＳＯＧ）を用いたスピンコート法により形成する。なお、ＣＶＤや、その他の埋め込み法により充填膜４０を形成してもよい。第１の横配線領域２６においては、横配線１２と基板１０との間の空洞が、充填膜４０で埋め尽くされる。また、第１の無配線領域２５も、充填膜４０で埋め込まれる。   As shown in FIG. 2I, a silicon oxide-based filling film 40 is formed on the substrate 10 and the horizontal wiring 12 by a spin coating method using spin-on-glass (SOG). The filling film 40 may be formed by CVD or other embedding methods. In the first lateral wiring region 26, the cavity between the lateral wiring 12 and the substrate 10 is filled with the filling film 40. Further, the first non-wiring region 25 is also filled with the filling film 40.

図２Ｊに示すように、２層目の縦配線を形成すべき第２の縦配線領域５０の充填膜４０をエッチング等により除去し、１層目の横配線１２を露出させる。同時に、２層目の横配線を形成すべき第２の横配線領域５１の充填膜４０の上面が、１層目の横配線１２の上面と同じ高さになるように、充填膜４０の表層部を除去する。２層目に縦配線及び横配線のいずれも形成されない第２の無配線領域５２には、１層目の横配線１２の上面よりも上に、充填膜４０が残っている。   As shown in FIG. 2J, the filling film 40 in the second vertical wiring region 50 where the second vertical wiring is to be formed is removed by etching or the like to expose the first horizontal wiring 12. At the same time, the surface layer of the filling film 40 is such that the upper surface of the filling film 40 in the second lateral wiring region 51 in which the second lateral wiring is to be formed is the same height as the upper surface of the first lateral wiring 12. Remove the part. In the second no-wiring region 52 where neither the vertical wiring nor the horizontal wiring is formed in the second layer, the filling film 40 remains above the upper surface of the first wiring 12.

図２Ｋに示すように、第２の縦配線領域５０に、導電膜５５及び縦配線用触媒膜５６を形成する。導電膜５５及び縦配線用触媒膜５６は、図２Ａ〜図２Ｃに示した１層目の導電膜２０及び縦配線用触媒膜２１と同じ方法で形成される。   As shown in FIG. 2K, a conductive film 55 and a vertical wiring catalyst film 56 are formed in the second vertical wiring region 50. The conductive film 55 and the vertical wiring catalyst film 56 are formed by the same method as the first conductive film 20 and the vertical wiring catalyst film 21 shown in FIGS. 2A to 2C.

図２Ｌに示すように、第２の横配線領域５１に、絶縁膜５７及び横配線用触媒膜５８を形成する。絶縁膜５７及び横配線用触媒膜５８は、図２Ｄ〜図２Ｅに示した１層目の絶縁膜３４及び横配線用触媒膜３５と同じ方法で形成される。   As shown in FIG. 2L, an insulating film 57 and a lateral wiring catalyst film 58 are formed in the second lateral wiring region 51. The insulating film 57 and the lateral wiring catalyst film 58 are formed by the same method as the first insulating film 34 and the lateral wiring catalyst film 35 shown in FIGS. 2D to 2E.

図２Ｍに示すように、第２の縦配線領域５０に２層目の縦配線１３を形成すると共に、第２の横配線領域５１、及びそれに連続する第２の縦配線領域５０に、２層目の横配線１４を形成する。２層目の縦配線１３及び横配線１４は、図２Ｆ〜図２Ｇに示した１層目の縦配線１１及び横配線１２と同じ方法で形成される。２層目の横配線１４を形成した時点では、２層目の横配線１４と絶縁膜５７との間は、空洞になっている。   As shown in FIG. 2M, the second vertical wiring 13 is formed in the second vertical wiring area 50, and two layers are formed in the second horizontal wiring area 51 and the second vertical wiring area 50 continuous thereto. The horizontal wiring 14 of eyes is formed. The vertical wiring 13 and the horizontal wiring 14 in the second layer are formed by the same method as the vertical wiring 11 and the horizontal wiring 12 in the first layer shown in FIGS. 2F to 2G. When the second lateral wiring 14 is formed, a space is formed between the second lateral wiring 14 and the insulating film 57.

１層目の充填膜４０及び２層目の横配線１４の上に、２層目の充填膜６０を形成する。２層目の横配線１４の下の空洞も、充填膜６０で埋め込まれる。   A second-layer filling film 60 is formed on the first-layer filling film 40 and the second-layer lateral wiring 14. The cavity below the second-level horizontal wiring 14 is also filled with the filling film 60.

図２Ｎに示すように、３層目の導電膜６５、絶縁膜６６、縦配線６７、及び横配線６８を、２層目と同様の方法で形成する。同様の方法で、４層目以上の配線を形成してもよい。   As shown in FIG. 2N, the third-layer conductive film 65, the insulating film 66, the vertical wiring 67, and the horizontal wiring 68 are formed in the same manner as in the second layer. A fourth or higher wiring layer may be formed by the same method.

図２Ｏに示すように、充填膜４０、６０を、フッ酸を用いたウェットエッチングにより除去する。なお、ＣＦ４等を用いたドライエッチングにより除去することも可能である。基板１０と１層目〜３層目の横配線１２、１４、６８との間が空洞になる。この空洞には、空気、不活性ガス等のガスが満たされるか、真空状態に保持される。さらに、配線全体の強度を高めるために、一部の配線部分には層間絶縁膜を残すことも可能である。 As shown in FIG. 2O, the filling films 40 and 60 are removed by wet etching using hydrofluoric acid. It is also possible to remove by dry etching using CF 4 or the like. A space is formed between the substrate 10 and the first to third horizontal wires 12, 14, 68. This cavity is filled with a gas such as air or an inert gas or is kept in a vacuum state. Furthermore, in order to increase the strength of the entire wiring, it is possible to leave an interlayer insulating film in a part of the wiring.

上記実施例１では、縦配線１１、１３、６７がカーボンナノチューブで形成され、横配線１２、１４、６８がグラファイトで形成される。カーボンナノチューブ及びグラファイトは、銅よりも３桁程度高い電流密度耐性を有し、バリスティック伝導等の優れた電気特性を示す。さらに、カーボンナノチューブ及びグラファイトは、高い熱伝導性を示す。このため、配線が微細化してもエレクトロマイグレーションの発生を抑制することができる。   In the first embodiment, the vertical wirings 11, 13, and 67 are formed of carbon nanotubes, and the horizontal wirings 12, 14, and 68 are formed of graphite. Carbon nanotubes and graphite have a current density tolerance that is about three orders of magnitude higher than copper, and exhibit excellent electrical characteristics such as ballistic conduction. Furthermore, carbon nanotubes and graphite exhibit high thermal conductivity. For this reason, even if the wiring is miniaturized, the occurrence of electromigration can be suppressed.

また、実施例１では、配線間が空洞で絶縁される。この空洞内は、空気、窒素やアルゴン等の不活性ガス等で満たされる。または、この空洞は真空状態に保持される。これらのガス、及び真空は、一般的な層間絶縁膜材料に比べて低い誘電率（比誘電率が１程度）を持つ。このため、寄生容量を低減させることができる。   Further, in the first embodiment, the wiring is insulated by a cavity. This cavity is filled with air, an inert gas such as nitrogen or argon, and the like. Alternatively, this cavity is kept in a vacuum state. These gases and vacuum have a low dielectric constant (relative dielectric constant is about 1) compared to a general interlayer insulating film material. For this reason, parasitic capacitance can be reduced.

実施例１では、縦配線用触媒膜２１の厚さを２．６ｎｍとし、横配線用触媒膜３５の厚さを４．５ｎｍとした。触媒膜２１、３５の好適な厚さは、カーボンナノチューブの成長条件に依存する。触媒膜が厚い場合には、触媒が微粒子状にならないため、その上にグラファイトは成長するが、カーボンナノチューブが下方に向かって成長することはない。従って、縦配線用触媒膜を、下方に向かってカーボンナノチューブが成長する程度まで薄くし、横配線用触媒膜は、カーボンナノチューブが成長しない程度まで厚くすることが好ましい。   In Example 1, the thickness of the vertical wiring catalyst film 21 was 2.6 nm, and the thickness of the horizontal wiring catalyst film 35 was 4.5 nm. A suitable thickness of the catalyst films 21 and 35 depends on the growth conditions of the carbon nanotubes. When the catalyst film is thick, since the catalyst does not become fine particles, graphite grows on the catalyst film, but the carbon nanotube does not grow downward. Therefore, it is preferable that the vertical wiring catalyst film is thinned to the extent that carbon nanotubes grow downward, and the horizontal wiring catalyst film is thickened to the extent that carbon nanotubes do not grow.

図３に、実施例１の変形例による配線構造体の１層目の配線の断面図を示す。この変形例においては、横配線領域２６の横配線１２の下側の表面から下方に向かってカーボンナノチューブ１１Ｂが成長している。カーボンナノチューブの成長の速さは、触媒膜が薄いほど速い。横配線領域２６内のカーボンナノチューブの成長速度が、縦配線領域２３内のカーボンナノチューブの成長速度に比べて十分遅い場合には、横配線領域２６に形成されるカーボンナノチューブ１１Ｂの長さが、縦配線領域２３に形成されるカーボンナノチューブ１１Ａの長さよりも短くなる。横配線１２が、カーボンナノチューブ１１Ｂの長さよりも高い位置まで持ち上げられるため、横配線領域２６に形成されたカーボンナノチューブ１１Ｂの下方の先端と、基板１０との間に空洞が生じる。このため、カーボンナノチューブ１１Ｂが、予期しない導電領域に接触することはない。   FIG. 3 is a cross-sectional view of the first layer wiring of the wiring structure according to the modification of the first embodiment. In this modification, the carbon nanotubes 11 </ b> B grow downward from the lower surface of the horizontal wiring 12 in the horizontal wiring region 26. Carbon nanotubes grow faster as the catalyst film is thinner. When the growth rate of the carbon nanotubes in the horizontal wiring region 26 is sufficiently slower than the growth rate of the carbon nanotubes in the vertical wiring region 23, the length of the carbon nanotubes 11B formed in the horizontal wiring region 26 is The length is shorter than the length of the carbon nanotubes 11 </ b> A formed in the wiring region 23. Since the horizontal wiring 12 is lifted to a position higher than the length of the carbon nanotube 11 </ b> B, a cavity is formed between the tip of the carbon nanotube 11 </ b> B formed in the horizontal wiring region 26 and the substrate 10. For this reason, the carbon nanotube 11B does not contact an unexpected conductive region.

図３に示した変形例のように、横配線領域２６にカーボンナノチューブが成長する場合であっても、その成長の速さが、縦配線領域２３のカーボンナノチューブの成長速度に比べて十分遅い場合には、実施例１の場合と同様に、横配線１２を中空に支持することができる。横配線を中空に支持するために、横配線領域２６のカーボンナノチューブの成長速度が、縦配線領域２３のカーボンナノチューブの成長速度の５０％以下になるように、膜厚及び成長条件を設定することが好ましい。   Even when carbon nanotubes grow in the horizontal wiring region 26 as in the modification shown in FIG. 3, the growth rate is sufficiently slower than the growth rate of the carbon nanotubes in the vertical wiring region 23. In the same manner as in the first embodiment, the horizontal wiring 12 can be supported in a hollow state. In order to support the horizontal wiring in a hollow state, the film thickness and the growth conditions are set so that the growth rate of the carbon nanotubes in the horizontal wiring region 26 is 50% or less of the growth rate of the carbon nanotubes in the vertical wiring region 23. Is preferred.

一例として、カーボンナノチューブの成長温度は、３００℃〜６００℃の範囲内とすることが好ましい。原料ガスとして、アセチレン、エチレン、メタン等の炭化水素や、エタノール、メタノール等のアルコールを用いることができる。原料ガスを希釈するガスとして、アルゴン、水素、窒素、またはヘリウムを用いることができる。成長時のガス圧は、一例として０．１ｋＰａ〜１０ｋＰａとすることができる。カーボンナノチューブの長さは、成長時間で制御することができる。例えば、成長時間は６０分程度とする。成長ガス中に添加ガスとして、酸素、水蒸気、アルコールを微量（例えば成長ガス圧の１％程度）混ぜてもよい。   As an example, the growth temperature of the carbon nanotube is preferably in the range of 300 ° C to 600 ° C. As the source gas, hydrocarbons such as acetylene, ethylene and methane, and alcohols such as ethanol and methanol can be used. Argon, hydrogen, nitrogen, or helium can be used as a gas for diluting the source gas. As an example, the gas pressure during growth can be set to 0.1 kPa to 10 kPa. The length of the carbon nanotube can be controlled by the growth time. For example, the growth time is about 60 minutes. Oxygen, water vapor, and alcohol may be mixed in the growth gas as additive gases (for example, about 1% of the growth gas pressure).

縦配線用触媒膜２１の厚さは、１ｎｍ〜５ｎｍの範囲内とし、横配線用触媒膜３５の厚さは、縦配線用触媒膜２１よりも厚く、かつ２ｎｍ〜５０ｎｍの範囲内とする。   The thickness of the vertical wiring catalyst film 21 is in the range of 1 nm to 5 nm, and the thickness of the horizontal wiring catalyst film 35 is thicker than the vertical wiring catalyst film 21 and in the range of 2 nm to 50 nm.

実施例１では、最終的に充填膜４０、６０を除去したが、充填膜４０、６０に、例えばポーラスシリカ等の低誘電率材料を用い、そのまま残存させてもよい。充填膜４０、６０を残存させると、配線の機械的強度を増すことができる。同様に、配線の一部分に充填材を用い、残る一部分を除去してもよい。この場合も、配線の機械的強度を高めることが可能となる。   In the first embodiment, the filling films 40 and 60 are finally removed. However, a low dielectric constant material such as porous silica may be used for the filling films 40 and 60 and left as they are. If the filling films 40 and 60 are left, the mechanical strength of the wiring can be increased. Similarly, a filler may be used for a part of the wiring and the remaining part may be removed. Also in this case, the mechanical strength of the wiring can be increased.

図４Ａ〜図４Ｆを参照して、実施例２による配線構造体の製造方法について説明する。なお、以下の説明においては、実施例１の製造方法との相違点に着目し、実施例１の製造方法と同一の工程については、説明を省略する場合がある。   With reference to FIG. 4A-FIG. 4F, the manufacturing method of the wiring structure by Example 2 is demonstrated. In the following description, paying attention to differences from the manufacturing method of Example 1, description of the same steps as those of the manufacturing method of Example 1 may be omitted.

図４Ａに示すように、基板１０の表面の、相互に離隔した複数の縦配線領域２３に、導電膜２０及び縦配線用触媒膜２１を形成する。１つの縦配線領域２３から他の縦配線領域２３まで連続する横配線領域２６には、基板１０の表面が露出している。   As shown in FIG. 4A, the conductive film 20 and the vertical wiring catalyst film 21 are formed in a plurality of vertical wiring regions 23 spaced from each other on the surface of the substrate 10. The surface of the substrate 10 is exposed in a horizontal wiring region 26 that continues from one vertical wiring region 23 to another vertical wiring region 23.

図４Ｂに示すように、横配線領域２６に、絶縁膜３４及び横配線用触媒膜３５を形成する。   As shown in FIG. 4B, an insulating film 34 and a lateral wiring catalyst film 35 are formed in the lateral wiring region 26.

図４Ｃに示すように、支持領域２７の横配線用触媒膜３５を除去し、絶縁膜３４を露出させる。支持領域２７は、横配線領域２６のうち、当該横配線領域２６に連続している縦配線領域２３のいずれからも離隔した領域に画定されている。横配線用触媒膜３５の除去には、例えばイオンミリングを用いることができる。なお、リフトオフ法を用いて、図４Ｃに示すようにパターニングされた横配線用触媒膜３５を形成してもよい。   As shown in FIG. 4C, the lateral wiring catalyst film 35 in the support region 27 is removed, and the insulating film 34 is exposed. The support region 27 is defined as a region separated from any of the vertical wiring regions 23 that are continuous to the horizontal wiring region 26 in the horizontal wiring region 26. For example, ion milling can be used to remove the lateral wiring catalyst film 35. Note that the lift-off method may be used to form the patterned lateral wiring catalyst film 35 as shown in FIG. 4C.

図４Ｄに示すように、支持領域２７に、支持用触媒膜３６を形成する。支持用触媒膜３６は、縦配線用触媒膜２１と同じ材料で形成され、その厚さも、縦配線用触媒膜２１と同一である。支持用触媒膜３６は、例えばリフトオフ法を用いてパターニングすることができる。   As shown in FIG. 4D, a support catalyst film 36 is formed in the support region 27. The supporting catalyst film 36 is formed of the same material as the vertical wiring catalyst film 21, and the thickness thereof is the same as that of the vertical wiring catalyst film 21. The supporting catalyst film 36 can be patterned using, for example, a lift-off method.

図４Ｅに示すように、横配線１２及び縦配線１１を形成する。このとき、支持領域２７にも、カーボンナノチューブの束で構成される支持部材１５が形成される。   As shown in FIG. 4E, the horizontal wiring 12 and the vertical wiring 11 are formed. At this time, the support member 15 composed of a bundle of carbon nanotubes is also formed in the support region 27.

図４Ｆに示すように、横配線１２の上に、２層目の導電膜５５、絶縁膜５７、縦配線１３及び横配線１４を形成する。２層目の１つの縦配線１３は、平面視において支持部材１５と重なる位置に配置される。   As shown in FIG. 4F, the second conductive film 55, the insulating film 57, the vertical wiring 13, and the horizontal wiring 14 are formed on the horizontal wiring 12. One vertical wiring 13 in the second layer is arranged at a position overlapping the support member 15 in plan view.

実施例２では、横配線１２が、縦配線１１のみではなく、支持部材１５によっても支持されている。縦配線１１の位置は、電子回路の設計上の要請から決まる。このため、縦配線１１の位置を、自由に設定することはできない。１本の横配線１２で接続すべき２つの縦配線１１の間隔が広い場合には、中空に支持されている横方向１２の機械的強度が弱くなる。実施例２のように、横配線１２を、支持部材１５で支持することにより、横配線１２の十分な機械的強度を維持することができる。   In the second embodiment, the horizontal wiring 12 is supported not only by the vertical wiring 11 but also by the support member 15. The position of the vertical wiring 11 is determined by the design requirements of the electronic circuit. For this reason, the position of the vertical wiring 11 cannot be set freely. When the distance between the two vertical wirings 11 to be connected by one horizontal wiring 12 is wide, the mechanical strength in the horizontal direction 12 that is supported hollowly becomes weak. By supporting the horizontal wiring 12 with the support member 15 as in the second embodiment, sufficient mechanical strength of the horizontal wiring 12 can be maintained.

２層目の縦配線１３を、１層目の横配線１２の中空部分に配置すると、上層の配線の重みによって、１層目の横配線１２が破壊されやすくなる。実施例２のように、２層目の縦配線１３の真下に、１層目の支持部材１５を配置することにより、上層配線の重みに耐えることが可能な十分な機械的強度を確保することができる。これにより、上層の縦配線１３の配置の自由度が高まる。   If the second-layer vertical wiring 13 is arranged in the hollow portion of the first-layer horizontal wiring 12, the first-layer horizontal wiring 12 is easily broken by the weight of the upper-layer wiring. As in the second embodiment, a sufficient mechanical strength capable of withstanding the weight of the upper layer wiring is ensured by disposing the first layer support member 15 directly below the second layer vertical wiring 13. Can do. Thereby, the freedom degree of arrangement | positioning of the vertical wiring 13 of an upper layer increases.

支持部材１５と基板１０との間に、絶縁膜３４が配置されているため、横配線１２が、支持部材１５を経由して、基板１０上の予期しない導電領域に電気的に接続されてしまうことはない。   Since the insulating film 34 is disposed between the support member 15 and the substrate 10, the horizontal wiring 12 is electrically connected to an unexpected conductive region on the substrate 10 via the support member 15. There is nothing.

図５に、実施例２の変形例による配線構造体の断面図を示す。２層目の横配線１４が、支持部材１７によって支持されている。支持部材１７の下端には、２層目の絶縁膜５７が接続されている。２層目の絶縁膜５７は、２層目の支持部材１７の真下に配置された１層目の支持部材１５によって補強されている。１層目の支持部材１５と２層目の絶縁膜５７との間には、１層目の横配線１２と同一の工程で形成されたダミー配線１６が配置されている。   FIG. 5 shows a cross-sectional view of a wiring structure according to a modification of the second embodiment. A second-layer horizontal wiring 14 is supported by a support member 17. A second insulating film 57 is connected to the lower end of the support member 17. The second-layer insulating film 57 is reinforced by the first-layer support member 15 disposed immediately below the second-layer support member 17. Between the first-layer support member 15 and the second-layer insulating film 57, a dummy wiring 16 formed in the same process as the first-layer horizontal wiring 12 is disposed.

このように、１層目の支持部材１５と２層目の支持部材１７とを、平面視において重なるように配置することにより、２層目の横配線１４を補強することができる。   In this manner, the second-layer horizontal wiring 14 can be reinforced by arranging the first-layer support member 15 and the second-layer support member 17 so as to overlap in plan view.

以上実施例に沿って本発明を説明したが、本発明はこれらに制限されるものではない。例えば、種々の変更、改良、組み合わせ等が可能なことは当業者に自明であろう。   Although the present invention has been described with reference to the embodiments, the present invention is not limited thereto. It will be apparent to those skilled in the art that various modifications, improvements, combinations, and the like can be made.

実施例１による配線構造体の斜視図である。1 is a perspective view of a wiring structure according to Example 1. FIG. （２Ａ）〜（２Ｅ）は、実施例１による配線構造体の製造途中段階における断面図である。(2A) to (2E) are cross-sectional views in the course of manufacturing the wiring structure according to the first embodiment. （２Ｆ）〜（２Ｈ）は、実施例１による配線構造体の製造途中段階における断面図である。(2F) to (2H) are cross-sectional views in the course of manufacturing the wiring structure according to the first embodiment. （２Ｉ）〜（２Ｋ）は、実施例１による配線構造体の製造途中段階における断面図である。(2I) to (2K) are cross-sectional views in the course of manufacturing the wiring structure according to the first embodiment. （２Ｌ）〜（２Ｍ）は、実施例１による配線構造体の製造途中段階における断面図である。(2L) to (2M) are cross-sectional views in the course of manufacturing the wiring structure according to the first embodiment. （２Ｎ）は、実施例１による配線構造体の製造途中段階における断面図であり、（２Ｏ）は、実施例１による配線構造体の断面図である。(2N) is a cross-sectional view in the process of manufacturing the wiring structure according to the first embodiment, and (2O) is a cross-sectional view of the wiring structure according to the first embodiment. 実施例１の変形例による配線構造体の断面図である。7 is a cross-sectional view of a wiring structure according to a modification of Example 1. FIG. （４Ａ）〜（４Ｄ）は、実施例２による配線構造体の製造途中段階における断面図である。(4A) to (4D) are cross-sectional views in the course of manufacturing the wiring structure according to the second embodiment. （４Ｅ）〜（４Ｆ）は、実施例２による配線構造体の製造途中段階における断面図である。(4E)-(4F) are sectional views in the course of manufacturing the wiring structure according to the second embodiment. 実施例２の変形例による配線構造体の断面図である。10 is a cross-sectional view of a wiring structure according to a modification of Example 2. FIG.

符号の説明Explanation of symbols

１０ 基板
１１ １層目の縦配線
１２ １層目の横配線
１３ ２層目の縦配線
１４ ２層目の横配線
１５ 支持部材
２０ 導電膜
２１ 縦配線用触媒膜
２２ レジストパターン
２３ 第１の縦配線領域
２５ 第１の無配線領域
２６ 第１の横配線領域
２７ 支持領域
３０ レジストパターン
３４ 絶縁膜
３５ 横配線用触媒膜
４０ 充填膜
５０ 第２の縦配線領域
５１ 第２の横配線領域
５２ 第２の無配線領域
５５ 導電膜
５６ 縦配線用触媒膜
５７ 絶縁膜
５８ 横配線用触媒膜
６０ 充填膜
６５ 導電膜
６６ 絶縁膜
６７ ３層目の縦配線
６８ ３層目の横配線 10 substrate 11 first layer vertical wiring 12 first layer horizontal wiring 13 second layer vertical wiring 14 second layer horizontal wiring 15 support member 20 conductive film 21 vertical wiring catalyst film 22 resist pattern 23 first vertical wiring Wiring area 25 First non-wiring area 26 First horizontal wiring area 27 Support area 30 Resist pattern 34 Insulating film 35 Lateral wiring catalyst film 40 Filling film 50 Second vertical wiring area 51 Second horizontal wiring area 52 2 non-wiring region 55 conductive film 56 vertical wiring catalyst film 57 insulating film 58 horizontal wiring catalyst film 60 filling film 65 conductive film 66 insulating film 67 third layer vertical wiring 68 third layer horizontal wiring

Claims (5)

基板表面の相互に離隔した２つの縦配線領域に、第１の厚さの縦配線用触媒膜を形成し、１つの該縦配線領域から他の縦配線領域まで連続する横配線領域に、該第１の厚さよりも厚い第２の厚さの横配線用触媒膜を形成する工程と、
前記縦配線用触媒膜及び横配線用触媒膜の上に、カーボンを含む構造体を気相成長させる工程と
を有し、
前記気相成長の初期段階には、前記縦配線用触媒膜及び横配線用触媒膜の上にグラファイトが形成され、その後、前記縦配線領域の前記グラファイトと前記基板との間にカーボンナノチューブが成長し、前記横配線領域の前記グラファイトが、前記縦配線領域に成長したカーボンナノチューブによって中空に支持されるように前記第１の厚さ及び第２の厚さが設定されている配線構造体の製造方法。 A catalyst film for vertical wiring having a first thickness is formed in two vertical wiring regions spaced apart from each other on the substrate surface, and the horizontal wiring region continuous from one vertical wiring region to another vertical wiring region Forming a lateral wiring catalyst film having a second thickness greater than the first thickness;
Vapor-phase-growing a structure containing carbon on the vertical wiring catalyst film and the horizontal wiring catalyst film,
In the initial stage of the vapor phase growth, graphite is formed on the vertical wiring catalyst film and the horizontal wiring catalyst film, and then carbon nanotubes grow between the graphite and the substrate in the vertical wiring region. And manufacturing the wiring structure in which the first thickness and the second thickness are set so that the graphite in the horizontal wiring region is supported in a hollow manner by the carbon nanotubes grown in the vertical wiring region. Method. 前記第１の厚さは１ｎｍから５ｎｍまでの範囲内であり、前記第２の厚さは２ｎｍから５０ｎｍまでの範囲内である請求項１に記載の配線構造体の製造方法。   2. The method for manufacturing a wiring structure according to claim 1, wherein the first thickness is in a range from 1 nm to 5 nm, and the second thickness is in a range from 2 nm to 50 nm. 基板の表面の複数の導電性領域の各々から延びる複数のカーボンナノチューブを含む縦配線と、
少なくとも２つの前記縦配線の一方の上端から他方の上端まで横方向に延びるグラファイトを含む横配線と
を有する配線構造体。 A vertical wiring including a plurality of carbon nanotubes extending from each of a plurality of conductive regions on the surface of the substrate;
A wiring structure having at least two horizontal wirings including graphite extending in a lateral direction from one upper end to the other upper end of the vertical wirings. 前記横配線と前記基板との間は真空である、または前記横配線と前記基板との間に気体が満たされている請求項３に記載の配線構造体。   The wiring structure according to claim 3, wherein a vacuum is formed between the horizontal wiring and the substrate, or a gas is filled between the horizontal wiring and the substrate. さらに、前記横配線の底面の一部から前記基板側に向かって延びる複数のカーボンナノチューブを含む支持部材と、
前記支持部材の下端と前記基板との間に配置された絶縁膜と
を有する請求項３または４に記載の配線構造体。 Further, a support member including a plurality of carbon nanotubes extending from a part of the bottom surface of the horizontal wiring toward the substrate side,
The wiring structure according to claim 3, further comprising an insulating film disposed between a lower end of the support member and the substrate.
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